CN113908808A - An MOF separation material in N2/O2Use in separations - Google Patents
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- 238000000926 separation method Methods 0.000 title claims abstract description 48
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- 238000001179 sorption measurement Methods 0.000 claims abstract description 47
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- 239000007789 gas Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- -1 MSK-96Cr Chemical compound 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 13
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- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000003795 desorption Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
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- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004904 shortening Methods 0.000 abstract 1
- 239000003463 adsorbent Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 6
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- 230000004913 activation Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000013291 MIL-100 Substances 0.000 description 3
- 238000003991 Rietveld refinement Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000013114 Co-MOF-74 Substances 0.000 description 2
- 239000013148 Cu-BTC MOF Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000013207 UiO-66 Substances 0.000 description 2
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N trimesic acid Natural products OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 2
- IGRCWJPBLWGNPX-UHFFFAOYSA-N 3-(2-chlorophenyl)-n-(4-chlorophenyl)-n,5-dimethyl-1,2-oxazole-4-carboxamide Chemical compound C=1C=C(Cl)C=CC=1N(C)C(=O)C1=C(C)ON=C1C1=CC=CC=C1Cl IGRCWJPBLWGNPX-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/12—Oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/102—Nitrogen
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Abstract
The invention discloses a MOF separation material in N2/O2Use in separations, N2/O2The separation being to produce O of high purity2Is an important method of the present invention. The invention relates to a metal-organic framework material based on chromium, namely MSK-96Cr, N2The adsorption capacity is 37.46 cm3•cm‑3，N2/O2The (10: 90, v/v) selectivity was 22.45 (298K and 1 bar). MSK-96Cr has high N2Adsorption capacity, thus also significantly shortening the gas adsorption equilibrium time; meanwhile, N is preferentially adsorbed by depending on unsaturated Cr metal sites2Can be in different N2/O2(50/50-79/21, v/v) concentration range for highly selective adsorption of N2Especially for N at higher oxygen concentrations2Adsorption of (2)Higher than other adsorption materials, for simulated air component N2/O2Separation efficiency at (79/21, v/v) 153 mmol.L‑1Has good oxygen production efficiency and has great application value for industrial production of high-purity oxygen.
Description
Technical Field
The invention relates to the field of metal organic framework materials, in particular to a MOF separation material in N2/O2Use in separation.
Background
High purity oxygen gas (>99%) is the most widely used commodity chemistry in the worldOne of the articles, for example, in medical, military, aerospace, semiconductor industries and plasma chemical applications. Currently, air separation is the production of high purity O2The most direct method mainly adopts a low-temperature distillation technology with high energy consumption and large investment cost, and only depends on N2(77.15K) and O2(90.15K) difference between boiling points. Although cryogenic distillation is used for large-scale air separation (>100 tons/year), but it is more economical and flexible to use membrane or adsorption separation processes for air separation for medium or portable oxygen supply.
Temperature/pressure swing adsorption (T/PSA) is a green technology process widely used today as an energy efficient air separation process. The PSA process needs to have a high N2 adsorption capacity and N2/O2The selective adsorbent, Li-LSX (lithium type low-silicon X type zeolite molecular sieve) shows good air separation yield, and Li-LSX has high N2 adsorption quantity and higher N2/O2Selectivity due to the presence of O in the channels of the lithium-containing molecular sieve2By contrast (N2 is-1.4D and O2 is-0.4D), N2Has a larger quadrupole moment, thereby generating stronger interaction, but O of Li-LSX is generated due to the fixed structure of the X-type molecular sieve taking Si, O and Al as main frameworks2Production efficiency has reached a limit and is difficult to break through (j.j. Potoff, j.i. Siepmann, AlChE j. 2001, 47, 1676.). Jeffrey R. Long (E.D. Bloch, L.J. Murray, W.L. Queen, S.Chavan, S.N. Maximoff, J.P. Bigi, R.Krishna, V.K. Peterson, F.Grandjean, G.J. Long, B.Smit, S.Bordiga, C.M. Brown, J.R. Long, J. Am. chem.Soc. 2011, 133, 14814; b) L.J. Murray, M.Dinca, J.Yan, S.Chavan, S.Bordiga, C.M. Brown, J.R. Long, J. Am. chem. Soc. 2010, 132, 7856.) and the like, propose to achieve O.2Highly selective adsorption method, and the porous materials adsorb O2Than N2More strongly, this is mainly due to the low valence metal centers (e.g., Cr (II) and Fe (II)) and O2Form strong O therebetween2Binding affinity, but in order to achieve high purity oxygen, a regeneration process by additional desorption or heating is required, thus consuming a large amount of energy.
To obtain N2 / O2The invention relates to a separation material with higher separation effect, which utilizes MOF material MSK-96Cr to N2 / O2Separation is carried out.
Disclosure of Invention
The invention relates to a MOF separation material in N2/O2The application in separation, its specific technological scheme is;
an MOF separation material in N2/O2The MOF separation material is MSK-96Cr, the MSK-96Cr is chromium with a microporous structure and MSK-96Cr synthesized by H3BTC, and the molecular formula of the MSK-96Cr is Cr12O-(OH/F)16(H2O)5[BTC]6·nH2O。
Specifically, the MSK-96Cr comprises 2 metal clusters, and the three metal clusters are Cr (1) and Cr (2), wherein the Cr (1) is a carbonyl oxide-centered tricyclic cluster, the structure of the tricyclic cluster is similar to that of the metal site in MIL-100Cr, and the Cr (2) is present in the other tricyclic cluster, and the two metal clusters can generate unsaturated metal sites.
Further, the MSK-96Cr comprises three pores, one closed cage with a narrow window dimension (1.2 a × 1.9 a), one elliptical window connected (7.2 a × 6.8 a), thereby forming a zigzag pore structure in MSK-96 Cr; during activation, the window size will increase after removal of the coordinated water molecules;
further, the high density Cr (III) unsaturated site and N of the MSK-96Cr2Form a strong interaction to realize N2/O2Separating;
the preparation method of the MSK-96Cr comprises the following steps:
mixing metallic chromium with a tricarboxylic acid, H3BTC is added into a polytetrafluoroethylene reaction kettle, and the water/methanol mixed solution and hydrofluoric acid are added into the reaction kettle and mixed. Stirring the mixture uniformly, sealing a polytetrafluoroethylene reactor in a stainless steel shell after stirring, putting the stainless steel shell into an oven for heating and keeping for a period of time, taking out a reaction kettle for naturally cooling to room temperature, and obtaining a light green product by reactionFiltering, washing with distilled water and methanol respectively, and drying to obtain MSK-96 Cr.
The metal chromium and H3The mol ratio of BTC is 1-2:1, and the mol ratio of the metallic chromium to the hydrofluoric acid is 1: 1-3;
stirring for 15-30min under the stirring condition of 298K;
the heating condition comprises the following steps: the temperature of the oven is raised from room temperature to 473-493K within 10-16 h and is kept at the temperature for 96 h;
the consumption of the distilled water is as follows: 200-280mL/g of product, the using amount of methanol is 200-280mL/g of product, and the washing times are 3-5 times;
the temperature of the oven was raised from room temperature to 483K over 12 h and kept at 483K for 96h, after which the reaction vessel was taken out and allowed to cool to room temperature. The pale green product from the reaction was filtered and then washed 3 times with 1 g/250 mL distilled water and 1 g/250 mL methanol at 353K to remove excess unreacted organic ligand. The resulting MSK-96Cr was then dried at 323K.
The technical effects are as follows:
the mechanism of the invention is that the d3 electronic configuration unsaturated metal (V (II) or Cr (III)) site has special binding affinity with N2, thereby preparing chromium and H3BTC-based microporous MOF MSK-96Cr with two active open Cr (III) sites and a more suitable pore environment and, based on optimized pore space, with on average more Cr (III) unsaturated sites per unit cell than MIL-100Cr (the best N has been reported to date)2/O2Separating material) has better N2 adsorption effect, and the content of Cr (III) unsaturated site in MSK-96Cr is 3.34 mmol-3Higher than 2.42 mmol/cm in MIL-100Cr-3(ii) a In addition, the moderate adsorption heat of the MSK-96Cr not only ensures that the MSK-96Cr has higher N2The adsorption capacity and greatly reduces the gas adsorption balance time; at the same time, N is preferentially adsorbed2The desired high purity O can be recovered directly from the adsorption cycle2And (5) producing the product.
Cr (1) carbonyl oxide-centered tricyclic cluster having a structure similar to that of the metal site in MIL-100Cr, and Cr (2) present in another site not presentIn the usual tricyclic cluster. Both metal clusters may produce unsaturated metal sites after removal of the terminal solvent molecule. Theoretically, the content of Cr (III) unsaturated sites in MSK-96Cr is higher than that in MIL-100Cr (3.34 vs.2.42 mmol. cm)-3). Thus, MSK-96Cr may exhibit a higher N2Adsorption capacity and N2/O2Adsorption selectivity, thereby obviously improving N2Separation performance.
MSK-96Cr has three types of pores: wells A, B and C; a is a closed cage with a narrow window dimension (1.2 a x 1.9 a) with B and C connected by an elliptical window (7.2 a x 6.8 a) to form a zigzag pore structure in MSK-96 Cr. Generally, during activation, the window size between B and C will increase after removal of the coordinated water molecules, favoring adsorption of the gas.
MSK-96Cr to N2Has a high adsorption capacity in different N2/O2(50/50-79/21, v/v) to N2Has good adsorption, especially to N under higher oxygen concentration2The adsorption amount of (A) is higher than that of other adsorption materials;
good selectivity of MSK-96Cr, compared with other adsorbents, in N2/O2The selectivity (50/50, v/v) can reach 13, which is far higher than the reported materials at present.
Has oxygen yield far higher than MIL-100Cr, in N2/O2(79/21, v/v) the yield obtainable was 153 mmol.L-1And the oxygen yield is much higher than that of MIL-100 Cr.
Drawings
FIG. 1 shows the framework structure and open metal sites of MSK-96 Cr;
FIG. 2 is a schematic diagram of three different types of cavities in MSK-96 Cr;
FIG. 3 a) Rietveld refinement XRD pattern of MSK-96 Cr; b) n of MSK-96Cr at 77K2Adsorption isotherms; c) Thermogravimetric curves of MSK-96Cr and MIL-100 Cr; d) PXRD patterns of the MSK-96Cr sample after being processed under different conditions;
FIG. 4N of various adsorption materials at 0-1bar2Drawing;
FIG. 5 shows the conventionalN of porous material2/O2Adsorption selectivity;
FIG. 6 shows multiple adsorbents at different N2/O2A mixture ratio breakthrough profile;
FIG. 7 MSK-96Cr at 5bar with different N2/O2The mixing ratio crosses the graph.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
MSK-96Cr preparation:
metallic chromium powder (104 mg, 2m mol) and H3BTC (280 mg, 1.34 m mol) were added to a 50 ml teflon reaction kettle, and then 10 ml of a methanol/water mixed solution (1:1, v/v) and 0.8 ml of hydrofluoric acid (4 m mol)) were added to the reaction kettle using a pipette. The mixture was stirred at 298K for 0.5 h, after stirring, the Teflon reactor was sealed in a stainless steel housing and placed in an oven. The temperature of the oven was raised from room temperature to 483K over 12 h and kept at 483K for 96h, after which the reaction vessel was taken out and allowed to cool to room temperature. The pale green product from the reaction was filtered and then washed 3 times with distilled water and methanol at 353K to remove excess unreacted organic ligand at a ratio of 1 g product/250 mL distilled water and 1 g product/250 mL methanol, respectively. The resulting MSK-96Cr product was then dried at 323K.
And (3) gas adsorption test:
the N2 and O2 single component gas adsorption isotherms and N2 adsorption kinetics curves were measured using an intelligent gravimetric analyzer (IGA 001, Hiden, UK). The nitrogen adsorption and desorption isotherms of the samples at 77K were measured using an APSP 2020 analyzer. Samples were at 523K and 1X 10 unless otherwise stated-5After 5 hours of mbar activation, further testing was carried out.
Structural analysis:
the structure of the MOF was accurately analyzed by Rietveld refinement (FIG. 3 a) using Topas software (CCDC: 2017985). The chemical formula of MSK-96Cr is determined as Cr12O-(OH/F)16(H2O)5[BTC]6·nH2O; the structure includes two forms of metal open sites: cr (1) and Cr (2) in a ratio of 1: 2;
MSK-96Cr has three types of pores: wells a, B and C, as shown in fig. 2: a is a closed cage with a narrow window dimension (1.2 a × 1.9 a), with B and C connected through an elliptical window (7.2 a × 6.8 a), thereby forming a zigzag pore structure in MSK-96 Cr. Generally, during activation, the window size between B and C will increase after removal of the coordinated water molecules.
The crystal data was calculated from the Rietveld refinement XRD pattern of MSK-96 Cr: rewp = 4.57%, Rwp = 4.84%, Rp = 4.72%, GOF = 1.06, a = b = 14.27 a, c = 30.98 a, α = β = 90 °, γ = 120 °; FIG. 3b N at 77K of MSK-96Cr2The adsorption isotherm is a type I adsorption isotherm, which indicates that MSK-96Cr is a microporous material.
Stability analysis
The TG curves of MSK-96Cr and MIL-100Cr show that the Cr (III) unsaturated site on MIL-100Cr is the key for binding gas molecules, but the coordinated water molecule on the Cr (III) site needs to be at extremely high temperature (523K, near the decomposition temperature of MIL-100 Cr) and high vacuum (10 is needed)-5mbar, turbomolecular pump required), whereas according to the TG results (fig. 3 c), MSK-96Cr remains stable up to 648K, well above the structural decomposition temperature of MIL-100Cr (ca. 573K); therefore, MSK-96Cr is more stable during the pretreatment process; in order to further verify the stability of the MSK-96Cr sample after being treated under different conditions, a certain amount of two samples are taken in water, acid and alkaline environments, boiling water, 12M HCl and 16M HNO3And 0.01M NaOH for 12 hours, and then the crystallinity of MSK-96Cr is detected by PXRD. It is shown that MSK-96Cr can maintain structural stability regardless of the presence of acid or alkali.
Example 2AN under the same pressure2Adsorption capacity
Different absorbing materials of MIL-100Cr, ZIF-8, UIO-66, Co-MOF-74, Cu-BTC, MIL-101Cr, 13X, Li-LSX and MSK-96Cr are mixed under 298K, the gas flow rate is 15ml/min, and N is2Partial pressures of 0.1 bar, 0.5 bar, 0.79 bar, different N of 1bar2/O2Mixed gas pair N2Comparison of separation capacities, the apparatus used for gas adsorption was the same as in example 1.
According to the results shown in FIG. 4, the respective pairs of adsorbing materials N were combined2As can be seen from the adsorption condition, MSK-96Cr shows the highest N in the pressure range2Adsorption capacity, N at 1bar2The adsorption capacity can reach 37.46 cm3•cm-3The adsorption capacity is remarkable.
Example 3 adsorption selectivity different adsorption materials MIL-100Cr, ZIF-8, UIO-66, Co-MOF-74, Cu-BTC, MIL-101Cr, 13X, Li-LSX and MSK-96Cr were subjected to gas adsorption experiments on the above samples using the same equipment as in example 1.
At 298K and 1bar, N2N partial pressure of 0.01 bar, 0.1 bar, 0.50 bar and 0.79 bar2 / O2(total pressure 1 bar) mixed gas pair N2The selectivity results are shown in figure 5 and table 1.
TABLE 1N of different adsorbents2/O2Selectivity is
The result shows that the MSK-96Cr has better adsorption selectivity than other adsorption materials under several partial pressure conditions.
Example 4 adsorbents at different N2/O2Penetration test of mixing ratio
The adsorbents MSK-96Cr, MIL-100Cr and 13X, Li-LSX are subjected to 298K 1bar at a flow rate of 15mL/miN is different from N2 / O2The mixture in the ratios (79: 21, 50:50, v/v) penetrated the experiment. The 4 adsorbent powders were first tableted with a tablet press at 4 MPa and then sieved through a stainless steel mesh screen to form granules of about 2 mm in diameter. The prepared MSK-96Cr, MIL-100Cr, Li-LSX and 13X samples are at 523K, 1X 10-5Activation is carried out for 12 h at mbar and then an adsorption column (phi 9.0X 150 mm) is loaded in an anhydrous environment. Before starting the test, the adsorption column was flushed with He gas at a flow rate of 15mL/min and a temperature of 373K, and then the test was carried out by switching the inlet gas to a mixed gas having a total gas flow rate of 15 mL/min. The spectrum of the gas at the outlet of the adsorption column was recorded using an online mass spectrometer (HPR-20 EGA, Hiden, UK, detection limit 0.01%) to obtain the final breakthrough curve.
By comparing the penetration graph 6, it can be seen that MSK-96Cr can effectively separate two N2 / O2Trapping N in mixture of volume ratio composition2Thereby obtaining O of high purity2。
While pure oxygen production was tested according to the above samples, the results are shown in table 2 below.
TABLE 2 adsorbents at various N2/O2Yield of pure oxygen at a ratio
MSK-96Cr has a pure oxygen yield much higher than MIL-100Cr and commercially used Li-LSX, and has great industrial application value for producing high-concentration oxygen.
Example 5N of MSK-96Cr at high pressure2/O2Specific separation experiment
To better achieve practical separation of MSK-96Cr, the MSK-96Cr was further investigated at high pressure for different concentrations of N, considering that the adsorbent typically experiences higher pressures and space velocities2 / O2The mixture is separated. Under 298K 5bar N2/O2(50: 50 and 79/21, v/v) Mixed gas breakthrough experiments were performed at a flow rate of 15 mL/min. The equipment and parameters used were the same as in example 4. The results of the breakthrough test are shown in FIG. 7, and high purity oxygen is also presentCan be produced with high separation efficiency under such conditions, and MSK-96Cr can be determined as N2 / O2Purifying the separated effective adsorbent.
Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, and other modifications or equivalent substitutions made by the technical solutions of the present invention by those of ordinary skill in the art should be covered within the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. An MOF separation material in N2/O2The MOF separation material is MSK-96Cr, and the molecular formula of the MSK-96Cr is Cr12O-(OH/F)16(H2O)5[BTC]6·nH2O, the MSK-96Cr passes through the unsaturated metal site pair N2/O2N in the mixed gas2Preferential adsorption is performed.
2. A MOF separation material of claim 1 at N2/O2The MSK-96Cr can be used for separating N2/O2Mixing N in the volume ratio of 1/99-79/212/O2And separating the mixed gas.
3. A MOF separation material of claim 1 at N2/O2The application of the method in the separation of the plant,
the lattice parameters of MSK-96Cr are a = b = 14.27 a, c = 30.98 a, α = β = 90 °, γ = 120 °.
4. A MOF separation material of claim 1 at N2/O2The application of the separation, the active metal Cr cluster has 2 kinds, namely Cr (1) and Cr (2), wherein the Cr (1) is a tricyclic cluster taking carbonyl oxide as a center, the Cr (2) exists in the other tricyclic cluster, and the two metal clusters can generate unsaturated metal sites.
5. A MOF separation material of claim 1 at N2/O2In the separation application, the MSK-96Cr comprises three holes, one closed cage with a narrow window size, and the other two closed cages are connected through an oval window, so that a zigzag hole structure is formed in the MSK-96 Cr.
6. A MOF separation material of claim 1 at N2/O2The application of the method in the separation of the plant,
the MSK-96Cr is chromium and H3BTC-based synthetic MOFs.
7. A MOF separation material according to any of claims 1 to 6, in N2/O2The application in the separation, the preparation method of the MSK-96Cr comprises the following steps:
mixing metallic chromium with a tricarboxylic acid, H3Adding BTC into a polytetrafluoroethylene reaction kettle, adding the water/methanol mixed solution and hydrofluoric acid into the reaction kettle, and mixing;
and (2) uniformly stirring the mixture, sealing a polytetrafluoroethylene reactor in a stainless steel shell after stirring is finished, putting the stainless steel shell into an oven for heating and keeping for a period of time, taking out the reaction kettle, naturally cooling to room temperature, filtering a light green product obtained by reaction, washing the product with distilled water and methanol respectively, and drying to obtain the MSK-96 Cr.
8. A MOF separation material of claim 6, at N2/O2Use in separation of said chromium metal from H3The mol ratio of BTC is 1-2:1, and the mol ratio of the metallic chromium to the hydrofluoric acid is 1: 1-3;
the stirring condition is 298K, and the stirring time is 15-30 min.
9. A MOF separation material of claim 6, at N2/O2The application in the separation comprises the following heating conditions: the temperature of the oven is raised from room temperature to 473-493K within 10-16 h and is kept at the temperature for 96 h;
the consumption of the distilled water is as follows: 200-280mL/g product, the amount of methanol is 200-280mL/g product, and the washing times are 3-5 times.
10. The MOF separation material N of claim 12/O2Use in separations, the MOF separation material can be used to produce pure oxygen without the need for additional desorption or regeneration processes.
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